9,9′-spirobixanthene derivatives for electroluminescent devices

ABSTRACT

The present invention relates to compounds suitable for use in electronic devices, and to electronic devices, especially organic electroluminescent devices, comprising these compounds.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a national stage application (under 35 U.S.C., §371)of PCT/EP2013/000593, filed Feb. 28, 2013, which claims benefit ofEuropean Application No. 12002073.0, filed Mar. 23, 2012, both of whichare incorporated herein by reference in their entirety.

The present invention relates to materials for use in electronicdevices, in particular in organic electroluminescent devices, and toelectronic devices, in particular organic electroluminescent devices,comprising these materials.

The structure of organic electroluminescent devices (OLEDs) in whichorganic semiconductors are employed as functional materials isdescribed, for example, in U.S. Pat. No. 4,539,507, U.S. Pat. No.5,151,629, EP 0676461 and WO 98/27136. The emitting materials employedhere are increasingly organometallic complexes which exhibitphosphorescence instead of fluorescence. For quantum-mechanical reasons,an up to four-fold energy and power efficiency is possible usingorganometallic compounds as phosphorescence emitters. In general,however, there is still a need for improvement in the case of OLEDs, inparticular also in the case of OLEDs which exhibit triplet emission(phosphorescence), for example with respect to efficiency, operatingvoltage and lifetime. In addition, it is desirable that the materialsused can be synthesised in high yield and purity.

The properties of phosphorescent OLEDs are determined not only by thetriplet emitters employed. In particular, the other materials used, suchas matrix materials, hole-blocking materials, electron-transportmaterials, hole-transport materials and electron- or exciton-blockingmaterials, are also of particular importance here. Improvements in thesematerials can thus also result in significant improvements in the OLEDproperties. For fluorescent OLEDs too, there is still a need forimprovement in the case of these materials and for emitters and matrixmaterials.

In accordance with the prior art, use is made of, inter alia, carbazolederivatives, for example in accordance with WO 2005/039246, US2005/0069729, JP 2004/288381, EP 1205527, WO 2008/086851 or WO2010/061315, indolocarbazole derivatives, for example in accordance withWO 2007/063754 or WO 2008/056746, indenocarbazole derivatives, forexample in accordance with WO 2010/136109, or dihydroacridinederivatives, for example in accordance with US 2010/0019658, as matrixmaterials for phosphorescent emitters in organic electroluminescentdevices. Further improvements are desirable here, and in relation to theefficiency, the lifetime and the thermal stability of the materials.

In accordance with the prior art, use is furthermore made of arylaminederivatives, in particular triarylamine derivatives andbis(diarylamino)aryl derivatives as hole-injection and hole-transportmaterials, for example based on spirobifluorenes (for example inaccordance with DE 102010045405).

The object of the present invention is the provision of compounds whichare suitable for use in a fluorescent or phosphorescent OLED, inparticular as matrix material or as hole-injection orhole-transport/electron-blocking material or exciton-blocking material,but also as hole-blocking material, matrix for fluorescent emitters oras fluorescent emitter. A further object of the present invention is toprovide further organic semiconductors for organic electroluminescentdevices in order thus to provide the person skilled in the art with agreater range of choice of materials for the production of OLEDs.

Surprisingly, it has been found that certain compounds described ingreater detail below achieve this object, are highly suitable for use inOLEDs and result in improvements in the organic electroluminescentdevice. The improvements here relate, in particular, to the lifetime,the efficiency and/or the operating voltage. The present inventiontherefore relates to these compounds and to electronic devices, inparticular organic electroluminescent devices, which comprise compoundsof this type.

The present invention relates to a compound of the formula (1),

where the following applies to the symbols and indices used:

-   X is on each occurrence, identically or differently, CR¹ or N; or    two adjacent X stand for S, O or NR¹, so that a five-membered ring    forms; or two adjacent X stand for a group of the following formula    (2), (3) or (4),

where ^ indicates the corresponding adjacent groups X in the formula(1);

X here stands for C if a group Ar or L is bonded to this group X;

-   V is on each occurrence, identically or differently, C(R¹)₂, NR¹, O    or S;-   Z is on each occurrence, identically or differently, CR¹ or N;-   Ar is on each occurrence, identically or differently, an aromatic or    heteroaromatic ring system having 5 to 40 aromatic ring atoms, which    may be substituted by one or more radicals R²; the group Ar and the    adjacent group X, which in this case stands for C, may also be    bridged to one another here by a single bond or a divalent group    selected from C(R²)₂, NR², O or S;-   L is on each occurrence, identically or differently, a single bond    or a divalent group;-   R¹, R² is selected on each occurrence, identically or differently,    from the group consisting of H, D, F, Cl, Br, I, CN, NO₂, N(Ar¹)₂,    N(R³)₂, C(═O)Ar¹, C(═O)R³, P(═O)(Ar¹)₂, P(Ar¹)₂, B(Ar¹)₂, Si(Ar¹)₃,    Si(R³)₃, a straight-chain alkyl, alkoxy or thioalkyl group having 1    to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl    group having 3 to 40 C atoms or an alkenyl or alkynyl group having 2    to 40 C atoms, each of which may be substituted by one or more    radicals R³, where one or more non-adjacent CH₂ groups may be    replaced by R³C═CR³, C≡C, Si(R³)₂, C═O, C═S, C═NR³, P(═O)(R³), SO,    SO₂, NR³, O, S or CONR³ and where one or more H atoms may be    replaced by D, F, Cl, Br, I, CN or NO₂, an aromatic or    heteroaromatic ring system having 5 to 60 aromatic ring atoms, which    may in each case be substituted by one or more radicals R³, an    aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms,    which may be substituted by one or more radicals R³, where two or    more adjacent substituents R¹ or R² may optionally form a monocyclic    or polycyclic, aliphatic, aromatic or heteroaromatic ring system,    which may be substituted by one or more radicals R³;-   Ar¹ is on each occurrence, identically or differently, an aromatic    or heteroaromatic ring system having 5-30 aromatic ring atoms, which    may be substituted by one or more non-aromatic radicals R³; two    radicals Ar¹ here which are bonded to the same N atom or P atom may    also be bridged to one another by a single bond or a bridge selected    from N(R³), C(R³)₂, O or S;-   R³ is selected on each occurrence, identically or differently, from    the group consisting of H, D, F, Cl, Br, I, CN, NO₂, N(R⁴)₂,    C(═O)R⁴, P(═O)(R⁴)₂, a straight-chain alkyl, alkoxy or thioalkyl    group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy    or thioalkyl group having 3 to 40 C atoms or an alkenyl or alkynyl    group having 2 to 40 C atoms, each of which may be substituted by    one or more radicals R⁴, where one or more non-adjacent CH₂ groups    may be replaced by R⁴C═CR⁴, C≡C, Si(R⁴)₂, C═O, C═S, C═NR⁴,    P(═O)(R⁴), SO, SO₂, NR⁴, O, S or CONR⁴ and where one or more H atoms    may be replaced by D, F, Cl, Br, I, CN or NO₂, an aromatic or    heteroaromatic ring system having 5 to 60 aromatic ring atoms, which    may in each case be substituted by one or more radicals R⁴, an    aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms,    which may be substituted by one or more radicals R⁴, or a    combination of these systems, where two or more adjacent    substituents R³ may optionally form a monocyclic or polycyclic,    aliphatic ring system, which may be substituted by one or more    radicals R⁴;-   R⁴ is selected on each occurrence, identically or differently, from    the group consisting of H, D, F, CN, an aliphatic hydrocarbon    radical having 1 to 20 C atoms, an aromatic or heteroaromatic ring    system having 5 to 30 aromatic ring atoms, in which one or more H    atoms may be replaced by D, F, Cl, Br, I or CN, where two or more    adjacent substituents R⁴ may form a mono- or polycyclic, aliphatic    ring system with one another;-   m is on each occurrence, identically or differently, 0 or 1;-   n is 0, 1, 2, 3, 4 or 5;    with the proviso that that for n=0, at least one substituent R¹ is    present which is selected from the group consisting of CN, N(Ar¹)₂,    C(═O)Ar¹, P(═O)(Ar¹)₂, P(Ar¹)₂, B(Ar¹)₂, Si(Ar¹)₃, Si(R³)₃ or an    aromatic or heteroaromatic ring system having 5 to 60 aromatic ring    atoms, which may in each case be substituted by one or more radicals    R₃;    compounds of the formula (1) in which n=0 and four substituents R¹    stand, identically or differently, for an optionally substituted    carbazole or diphenylamine, which is in each case bonded to the    skeleton via the nitrogen atom, are excluded from the invention.

An aryl group in the sense of this invention contains 6 to 60 C atoms; aheteroaryl group in the sense of this invention contains 2 to 60 C atomsand at least one heteroatom, with the proviso that the sum of C atomsand heteroatoms is at least 5. The heteroatoms are preferably selectedfrom N, O and/or S. An aryl group or heteroaryl group here is taken tomean either a simple aromatic ring, i.e. benzene, or a simpleheteroaromatic ring, for example pyridine, pyrimidine, thiophene, etc.,or a condensed (anellated) aryl or heteroaryl group, for examplenaphthalene, anthracene, phenanthrene, quinoline, isoquinoline, etc.Aromatic groups which are linked to one another by a single bond, suchas, for example, biphenyl, are, by contrast, not referred to as aryl orheteroaryl group, but instead as aromatic ring system.

An aromatic ring system in the sense of this invention contains 6 to 60C atoms in the ring system. A heteroaromatic ring system in the sense ofthis invention contains 2 to 60 C atoms and at least one heteroatom inthe ring system, with the proviso that the sum of C atoms andheteroatoms is at least 5. The heteroatoms are preferably selected fromN, O and/or S. For the purposes of this invention, an aromatic orheteroaromatic ring system is intended to be taken to mean a systemwhich does not necessarily contain only aryl or heteroaryl groups, butinstead in which, in addition, a plurality of aryl or heteroaryl groupsmay be connected by a non-aromatic unit, such as, for example, a C, N orO atom. Thus, for example, systems such as fluorene,9,9′-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether,stilbene, etc., are also intended to be taken to be aromatic ringsystems for the purposes of this invention, as are systems in which twoor more aryl groups are connected, for example, by a short alkyl group.

For the purposes of the present invention, an aliphatic hydrocarbonradical or an alkyl group or an alkenyl or alkynyl group, which maycontain 1 to 40 C atoms and in which, in addition, individual H atoms orCH₂ groups may be substituted by the above-mentioned groups, ispreferably taken to mean the radicals methyl, ethyl, n-propyl, i-propyl,n-butyl, i-butyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl,neopentyl, cyclopentyl, n-hexyl, neohexyl, cyclohexyl, n-heptyl,cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl,pentafluoroethyl, 2,2,2-trifluoroethyl, ethenyl, propenyl, butenyl,pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl,octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl,heptynyl or octynyl. An alkoxy group having 1 to 40 C atoms ispreferably taken to mean methoxy, trifluoromethoxy, ethoxy, n-propoxy,i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentoxy, s-pentoxy,2-methylbutoxy, n-hexoxy, cyclohexyloxy, n-heptoxy, cycloheptyloxy,n-octyloxy, cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy and2,2,2-trifluoroethoxy. A thioalkyl group having 1 to 40 C atoms is takento mean, in particular, methylthio, ethylthio, n-propylthio,i-propylthio, n-butylthio, i-butylthio, s-butylthio, t-butylthio,n-pentylthio, s-pentylthio, n-hexylthio, cyclohexylthio, n-heptylthio,cycloheptylthio, n-octylthio, cyclooctylthio, 2-ethylhexylthio,trifluoromethylthio, pentafluoroethylthio, 2,2,2-trifluoroethyl-thio,ethenylthio, propenylthio, butenylthio, pentenylthio, cyclopentenylthio,hexenylthio, cyclohexenylthio, heptenylthio, cycloheptenylthio,octenylthio, cyclooctenylthio, ethynylthio, propynylthio, butynylthio,pentynylthio, hexynylthio, heptynylthio or octynylthio. In general,alkyl, alkoxy or thioalkyl groups in accordance with the presentinvention may be straight-chain, branched or cyclic, where one or morenon-adjacent CH₂ groups may be replaced by the above-mentioned groups;furthermore, one or more H atoms may also be replaced by D, F, Cl, Br,I, CN or NO₂, preferably F, Cl or CN, further preferably F or CN,particularly preferably CN.

An aromatic or heteroaromatic ring system having 5-60 aromatic ringatoms, which may also in each case be substituted by the above-mentionedradicals R² or a hydrocarbon radical and which may be linked via anydesired positions on the aromatic or heteroaromatic ring system, istaken to mean, in particular, groups derived from benzene, naphthalene,anthracene, benzanthracene, phenanthrene, pyrene, chrysene, perylene,fluoranthene, naphthacene, penta-cene, benzopyrene, biphenyl,biphenylene, terphenyl, triphenylene, fluorene, spirobifluorene,dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- ortrans-indenofluorene, cis- or trans-indenocarbazole, cis- ortrans-indolocarbazole, truxene, isotruxene, spirotruxene,spiroisotruxene, furan, benzofuran, isobenzofuran, dibenzofuran,thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole,indole, isoindole, carbazole, pyridine, quinoline, isoquinoline,acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline,benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole,imidazole, benzimidazole, naphthimidazole, phenanthrimi-dazole,pyridimidazole, pyrazinimidazole, quinoxalinimidazole, oxazole,benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole,1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine,hexaazatriphenylene, benzo-pyridazine, pyrimidine, benzopyrimidine,quinoxaline, 1,5-diazaanthracene, 2,7-diazapyrene, 2,3-diazapyrene,1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene,4,5,9,10-tetraazaperylene, pyrazine, phenazine, phenoxazine,phenothiazine, fluorubin, naphthyridine, azacarbazole, benzocarboline,phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole,1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole,1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole,1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine,tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine,purine, pteridine, indolizine and benzothiadiazole or groups derivedfrom combination of these systems.

In an embodiment of the invention, compounds of the formula (1) in whichR¹ stands, identically or differently, for carbazole or for asubstituted carbazole, which is in each case bonded to the skeleton viathe nitrogen atom, or for diphenylamine or for a substituteddiphenylamine are excluded from the invention.

In a preferred embodiment of the invention, X stands, identically ordifferently on each occurrence, for CR¹ or N, where a maximum of onegroup X per ring stands for N; or two adjacent groups X stand for agroup of the formula (2), (3) or (4), in particular formula (3), where Zstands, identically or differently on each occurrence, for CR¹ and Vstands, identically or differently on each occurrence, for NR¹ orC(R¹)₂. Furthermore preferably, adjacent radicals R¹ which are presenton X do not form a ring with one another.

Particularly preferably, X stands, identically or differently on eachoccurrence, for CR¹.

Preference is furthermore given to compounds of the following formulae(1a), (1b), (1c) and (1d),

where the symbols and indices used have the meanings given above.

Particular preference is given to compounds of the above-mentionedformula (1) where n=0, i.e. compounds of the above-mentioned formula(1a).

Preference is furthermore given to compounds where n=1 and m=0, inparticular compounds of the following formulae (1e), (1f) and (1g), andcompounds where n=1, one m=0 and the other m=1 and L=single bond, inparticular compounds of the following formulae (1h), (1i) and (1j),

where the symbols us formula (1d) the meanings given above.

In a preferred embodiment of the invention, the group L stands,identically or differently on each occurrence, for a straight-chainalkylene or alkylidene group having 1 to 10 C atoms or a branched orcyclic alkylene or alkylidene group having 3 to 40 C atoms or analkenylene or alkynylene group having 2 to 40 C atoms, which may besubstituted by in each case one or more radicals R³, where one or morenon-adjacent CH₂ groups may be replaced by —R³C═CR³—, —C≡C—, Si(R³)₂,C═O, —O—, —S— or —CONR³— and where one or more H atoms may be replacedby D, F, Cl, Br, I, CN or NO₂, or P(R³), P(═O)(R³), N(Ar); or L is asingle bond.

Particularly preferred embodiments of the compounds of the formula (1)or (1a) are the compounds of the following formula (5) and particularlypreferred embodiments of the compounds of the formula (1b), (1c) and(1d) are the compounds of the following formulae (6), (7) and (8),

where the symbols and indices used have the meanings given above.

Furthermore, groups of the formula (2), (3) or (4) can be condensed on,as depicted below by way of example by the formulae (9), (10), (11) and(12) with condensed-on groups of the formula (3),

where the symbols and indices used have the meanings given above. It maybe preferred here, for V═C(R¹)₂, for the two radicals R¹ to form a ringwith one another and thus to form a spiro system.

In a preferred embodiment of the invention, a maximum of twosubstituents R¹ are not equal to H or D.

Particularly preferred embodiments of the structures of the formula (5)are the structures of the formulae (5a) to (5u),

where the symbols and indices used have the meanings given above.

Particularly preferred structures are the structures of theabove-mentioned formulae (5a), (5b), (5c), (5d), (5h), (5l), (5m) and(5u).

Particular preference is also given to structures of the above-mentionedformulae which contain two groups R¹, where one group R¹ is ahole-transporting unit and the other group R¹ is anelectron-transporting unit. The hole-transporting unit R¹ here is, inparticular, an optionally substituted carbazole group or a derivativethereof or an optionally substituted diarylamino group or triarylaminogroup. The electron-transporting unit R¹ is, in particular, anoptionally substituted electron-deficient heteroaryl group, inparticular an optionally substituted triazine or pyrimidine, an aromaticketone —C(═O)Ar¹ or an aromatic phosphine oxide —P(═O)(Ar¹)₂.

In a preferred embodiment of the invention, R¹ and R² in theabove-mentioned formulae are selected, identically or differently oneach occurrence, from the group consisting of H, D, F, Cl, Br, CN,N(Ar¹)₂, C(═O)Ar¹, P(═O)(Ar¹)₂, a straight-chain alkyl or alkoxy grouphaving 1 to 10 C atoms or a branched or cyclic alkyl or alkoxy grouphaving 3 to 10 C atoms or an alkenyl or alkynyl group having 2 to 10 Catoms, each of which may be substituted by one or more radicals R³,where one or more non-adjacent CH₂ groups may be replaced by O and whereone or more H atoms may be replaced by D or F, an aromatic orheteroaromatic ring system having 5 to 30 aromatic ring atoms, which mayin each case be substituted by one or more radicals R³.

In a particularly preferred embodiment of the invention, R¹ and R² inthe above-mentioned formulae are selected, identically or differently oneach occurrence, from the group consisting of H, D, F, Cl, Br, CN, astraight-chain alkyl group having 1 to 5 C atoms or a branched or cyclicalkyl group having 3 to 10 C atoms, where one or more H atoms may bereplaced by D or F, an aromatic or heteroaromatic ring system having 5to 18 aromatic ring atoms, which may in each case be substituted by oneor more radicals R³.

In compounds where n=0, at least one group R¹ stands, as describedabove, for a substituent which is selected from the group consisting ofCN, N(Ar¹)₂, C(═O)Ar¹, P(═O)(Ar¹)₂, P(Ar¹)₂, B(Ar¹)₂, Si(Ar¹)₃, Si(R³)₃,an aromatic or heteroaromatic ring system having 5 to 60 aromatic ringatoms, which may in each case be substituted by one or more radicals R³.This substituent is preferably selected from the group consisting ofN(Ar¹)₂, C(═O)Ar¹, P(═O)(Ar¹)₂ or an aromatic or heteroaromatic ringsystem having 5 to 40, particularly preferably having 5 to 18 aromaticring atoms, which may in each case be substituted by one or moreradicals R³.

For compounds which are processed by vacuum evaporation, the alkylgroups preferably have not more than five C atoms, particularlypreferably not more than 4 C atoms, very particularly preferably notmore than 1 C atom. For compounds which are processed from solution,compounds which are substituted by alkyl groups, in particular branchedalkyl groups, having up to 10 C atoms or which are substituted byoligoarylene groups, for example ortho-, meta-, para- or branchedterphenyl or quaterphenyl groups, are also suitable.

Preferred groups Ar are selected from aromatic or heteroaromatic ringsystems having 5 to 24 aromatic ring atoms, which may in each case besubstituted by one or more radicals R³. Particularly preferred groups Arare selected from benzene, ortho-, meta- or para-biphenyl, ortho-,meta-, para- or branched terphenyl, ortho-, meta- para- or branchedquaterphenyl, 1- or 2-naphthyl, pyrrole, furan, thiophene, indole,benzofuran, benzothiophene, carbazole, dibenzofuran, dibenzothiophene,pyridine, pyrimidine, pyrazine, pyridazine, triazine, anthracene,phenanthrene, pyrene, benzanthracene or combinations of two or three ofthese groups, each of which may be substituted by one or more radicalsR³.

If R¹ or R² stand for an aromatic or heteroaromatic ring system, this ispreferably selected, identically or differently on each occurrence, fromthe same groups as indicated above as preferred groups for Ar.

If the compounds of the formula (1) or the preferred embodiments areused as electron-transport material, it is preferred for at least one ofthe radicals R¹, R² and/or Ar to stand for an electron-deficientheteroaromatic ring system or —C(═O)Ar¹ or —P(═O)(Ar¹)₂.Electron-deficient heteroaromatic ring systems are in accordance withthe invention five-membered heteroaromatic ring systems having at leasttwo heteroatoms or six-membered heteroaromatic ring systems, onto whichone or more aromatic or heteroaromatic groups may in each case also becondensed, for example substituted or unsubstituted imidazoles,pyrazoles, thiazoles, oxazoles, oxadiazoles, triazoles, pyridines,pyrazines, pyrimidines, pyridazines, triazines, benzimidazoles, etc., inparticular those as shown below.

If the compound according to the invention is employed as matrixmaterial for a phosphorescent emitter or as electron-transport material,at least one substituent R¹ and/or R² or a monovalent group Ar ispreferably an electron-deficient group, in particular selected fromstructures of the following formulae (13) to (16) for R¹ or R² or theformulae (17), (18) or (19) for Ar,

and/or at least one divalent or trivalent group Ar preferably stands fora group of the following formulae (17) to (19),

where R⁴ and m have the meaning given above, * indicates the position ofthe bonding of the group of the formula (13) to (19) and furthermore:

-   A is on each occurrence, identically or differently, CR⁴ or N, with    the proviso that one, two or three groups A stand for N;-   Ar² is, identically or differently on each occurrence, a divalent    aromatic or heteroaromatic ring system having 5 to 16 C atoms, which    may be substituted by one or more radicals R⁴.

In a particularly preferred embodiment of the invention, at least onesubstituent R¹, R² or Ar stands for a group of the above-mentionedformula (13), and/or at least one group Ar stands for a group of theabove-mentioned formulae (17) to (19), where in each case two or threesymbols A stand for N and the other symbols A stand for CR⁴.Particularly preferred groups R¹, R² or Ar are therefore the groups ofthe following formulae (20) to (26), and particularly preferred groupsAr are the groups of the following formulae (27) to (34),

where the symbols and indices used have the meanings given above.

If R¹, R² or Ar stands for a group of the formula (20), R⁴ in this groupthen preferably stands for an aromatic or heteroaromatic ring systemhaving 5 to 24 aromatic ring atoms, which may be substituted by one ormore radicals R⁵, in particular for phenyl, ortho-, meta- orpara-biphenyl, ortho-, meta-, para- or branched terphenyl or ortho-,meta-, para- or branched quaterphenyl.

If R¹, R² or Ar stands for a group of the formula (21) to (34), R⁴ inthese groups then preferably stands, identically or differently on eachoccurrence, for H, D or an aromatic or heteroaromatic ring system having5 to 24 aromatic ring atoms, which may be substituted by one or moreradicals R⁵, in particular for H or phenyl, ortho-, meta- orpara-biphenyl, ortho-, meta-, para- or branched terphenyl or ortho-,meta-, para- or branched quaterphenyl.

If the compound according to the invention is employed as matrixmaterial for a phosphorescent emitter, as hole-transport material or aselectron- or exciton-blocking material, at least one substituent R¹, R²or Ar is preferably selected from the group consisting of triarylaminederivatives, carbazole derivatives, indenocarbazole derivatives,indolocarbazole derivatives, azacarbazole derivatives, indolederivatives, furan derivatives, benzofuran derivatives, dibenzofuranderivatives, thiophene derivatives, benzothiophene derivatives ordibenzothiophene derivatives, each of which may be substituted by one ormore radicals R³, or at least one substituent R¹ or R² stands for—N(Ar¹)₂. These groups are preferably selected from the groups of thefollowing formulae (35) to (49),

where the symbols used have the meanings given above and furthermore:E is selected from the group consisting of C(R³)₂, NR³, O or S;G is selected from the group consisting of NR³, O or S.

In a further preferred embodiment of the invention, the symbols R¹ andR² in the compounds according to the invention which do not stand for agroup of the above-mentioned formulae (13) to (49) stand for H or D.

The preferred embodiments mentioned above can be combined with oneanother as desired. In a particularly preferred embodiment of theinvention, the above-mentioned preferences occur simultaneously.

If the compounds of the formula (1) or the preferred embodiments areused as matrix material for a phosphorescent emitter, it is preferredfor the compound to contain no condensed aryl or heteroaryl groups inwhich more than two six-membered rings are condensed directly onto oneanother. In particular, it is preferred for the radicals R¹, R² and Arto contain no condensed aryl or heteroaryl group in which two or moresix-membered rings are condensed directly onto one another and for twoadjacent groups X not to stand for a group of the formula (2) or (4).The compound of the formula (1) particularly preferably containsabsolutely no condensed aryl or heteroaryl groups in which six-memberedrings are condensed directly onto one another.

If the compounds of the formula (1) or the preferred embodiments areused as matrix material for a fluorescent emitter or as fluorescentemitter, it is preferred for at least one of the radicals R¹ and/or R²to contain a group which is selected from naphthalene, anthracene,phenanthrene, pyrene and/or benzanthracene, each of which may also besubstituted by the above-mentioned groups, and/or for two adjacentgroups X at least on one of the aromatic rings to stand for a group ofthe formula (2) or (4).

Examples of preferred compounds in accordance with the embodiments shownabove are the compounds of the following structures 1 to 109.

The compounds according to the invention can be prepared by the routeoutlined in Scheme 1.

The metallation of a 2-halogen-substituted diaryl ether (A), where thehalogen is preferably bromine, using reactive metals (for examplemagnesium by the Grignard method) or using organolithium compounds,followed by addition onto mono-, di or polyhalogenated xanthone (B) andsubsequent acid-catalysed cyclisation of the intermediate alcoholateleads to the corresponding halogen-substituted spiro-9,9-bixanthenes (C)(Scheme 1). Hal here stands for a halogen and R for a substituent asdefined above for R¹.

The halides, in particular bromides, (C) formed in this way cansubsequently be reacted further by methods familiar to the personskilled in the art, such as, for example, C—C coupling, such as Suzuki,Negishi, Yamamoto, Grignard Cross, Stille, Heck coupling, etc., or C—Ncoupling, such as Buchwald or Ullmann coupling, sililyation,phosphanylation, boranylation, polycondensation, etc.

The present invention furthermore relates to a process for thepreparation of a compound of the formula (1), comprising the reactionsteps:

-   a) synthesis of a halogen-substituted spiro-9,9-bixanthene; and-   b) reaction of the halogen-substituted spiro-9,9-bixanthene in a C—C    coupling, such as Suzuki, Negishi, Yamamoto, Grignard-Cross, Stille,    Heck coupling, etc., or C—N coupling, such as Buchwald or Ullmann    coupling, sililyation, phosphanylation, boranylation,    polycondensation, etc. . . . .

The compounds according to the invention described above, in particularcompounds which are substituted by reactive leaving groups, such asbromine, iodine, chlorine, boronic acid or boronic acid ester, or byreactive, polymerisable groups, such as olefins, styrenes, acrylates oroxetanes, can be used as monomers for the generation of correspondingoligomers, dendrimers or polymers. The oligomerisation or polymerisationhere preferably takes place via the halogen functionality or the boronicacid functionality or via the polymerisable group. It is furthermorepossible to crosslink the polymers via groups of this type. Thecompounds and polymers according to the invention can be employed ascrosslinked or uncrosslinked layer.

The invention therefore furthermore relates to oligomers, polymers ordendrimers containing one or more of the compounds according to theinvention indicated above, where one or more bonds from the compoundaccording to the invention to the polymer, oligomer or dendrimer arepresent at one or more positions instead of substituents. Depending onthe linking of the compound according to the invention, this forms aside chain of the oligomer or polymer or is linked in the main chain orforms the core of a dendrimer. The polymers, oligomers or dendrimers maybe conjugated, partially conjugated or non-conjugated. The oligomers orpolymers may be linear, branched or dendritic. The same preferences asdescribed above apply to the recurring units of the compounds accordingto the invention in oligomers, dendrimers and polymers.

For the preparation of the oligomers or polymers, the monomers accordingto the invention are homopolymerised or copolymerised with furthermonomers. Preference is given to homopolymers or copolymers in which theunits of the formula (1) or the preferred embodiments indicated aboveare present to the extent of 0.01 to 99.9 mol %, preferably 5 to 90 mol%, particularly preferably 20 to 80 mol %. Suitable and preferredcomonomers which form the polymer backbone are selected from fluorenes(for example in accordance with EP 842208 or WO 2000/22026),spirobifluorenes (for example in accordance with EP 707020, EP 894107 orWO 2006/061181), para-phenylenes (for example in accordance with WO92/18552), carbazoles (for example in accordance with WO 2004/070772 orWO 2004/113468), thiophenes (for example in accordance with EP 1028136),dihydrophenanthrenes (for example in accordance with WO 2005/014689),cis- and trans-indenofluorenes (for example in accordance with WO2004/041901 or WO 2004/113412), ketones (for example in accordance withWO 2005/040302), phenanthrenes (for example in accordance with WO2005/104264 or WO 2007/017066) or also a plurality of these units. Thepolymers, oligomers and dendrimers may also contain further units, forexample hole-transport units, in particular those based ontriarylamines, and/or electron-transport units. In addition, thepolymers may contain triplet emitters, either copolymerised or mixed inas a blend. In particular, the combination of the oligomers, polymers ordendrimers according to the invention with triplet emitters leads toparticularly good results.

The compounds according to the invention are suitable for use in anelectronic device, in particular in an organic electroluminescentdevice.

The present invention therefore furthermore relates to the use of acompound according to the invention in an electronic device, inparticular in an organic electroluminescent device.

The present invention still furthermore relates to an electronic devicecomprising at least one compound according to the invention.

An electronic device in the sense of the present invention is a devicewhich comprises at least one layer which comprises at least one organiccompound. The component may also comprise inorganic materials or alsolayers which are built up entirely from inorganic materials.

The electronic device is preferably selected from the group consistingof organic electroluminescent devices (OLEDs), organic integratedcircuits (O-ICs), organic field-effect transistors (O-FETs), organicthin-film transistors (O-TFTs), organic light-emitting transistors(O-LETs), organic solar cells (O-SCs), dye-sensitised organic solarcells (DSSCs), organic optical detectors, organic photoreceptors,organic field-quench devices (O-FQDs), light-emitting electrochemicalcells (LECs), organic laser diodes (O-lasers) and “organic plasmonemitting devices” (D. M. Koller et al., Nature Photonics 2008, 1-4), butpreferably organic electroluminescent devices (OLEDs), particularlypreferably phosphorescent OLEDs.

The organic electroluminescent device comprises cathode, anode and atleast one emitting layer. Apart from these layers, it may also comprisefurther layers, for example in each case one or more hole-injectionlayers, hole-transport layers, hole-blocking layers, electron-transportlayers, electron-injection layers, exciton-blocking layers,electron-blocking layers and/or charge-generation layers. Interlayers,which have, for example, an exciton-blocking function, may likewise beintroduced between two emitting layers. However, it should be pointedout that each of these layers does not necessarily have to be present.The organic electroluminescent device here may comprise one emittinglayer, or it may comprise a plurality of emitting layers. If a pluralityof emission layers are present, these preferably have in total aplurality of emission maxima between 380 nm and 750 nm, resultingoverall in white emission, i.e. various emitting compounds which areable to fluoresce or phosphoresce are used in the emitting layers.Particular preference is given to systems having three emitting layers,where the three layers exhibit blue, green and orange or red emission(for the basic structure see, for example, WO 2005/011013). The organicelectroluminescent device according to the invention may also be atandem OLED, in particular also for white-emitting OLEDs.

The compound according to the invention in accordance with theembodiments indicated above can be employed in various layers, dependingon the precise structure. Preference is given to an organicelectroluminescent device comprising a compound of the formula (1) orthe preferred embodiments indicated above as matrix material forfluorescent or phosphorescent emitters and/or as fluorescent emitters,in particular for blue-fluorescent emitters, and/or in anelectron-blocking or exciton-blocking layer and/or in a hole-transportlayer and/or in a hole-blocking layer and/or in an electron-transportlayer, depending on the precise substitution.

In a further embodiment of the invention, the organic electroluminescentdevice comprises the compound according to the invention in an opticalcoupling-out layer. An optical coupling-out layer here is taken to meana layer which is not located between the anode and the cathode, butinstead is applied to an electrode outside the actual device, forexample between an electrode and a substrate, in order to improve theoptical coupling-out.

In a preferred embodiment of the invention, the compound according tothe invention is employed as matrix material for a fluorescent orphosphorescent compound, in particular for a phosphorescent compound, inan emitting layer. The organic electroluminescent device here maycomprise one emitting layer, or it may comprise a plurality of emittinglayers, where at least one emitting layer comprises at least onecompound according to the invention as matrix material.

If the compound according to the invention is employed as matrixmaterial for an emitting compound in an emitting layer, it is preferablyemployed in combination with one or more phosphorescent materials(triplet emitters). Phosphorescence in the sense of this invention istaken to mean the luminescence from an excited state having relativelyhigh spin multiplicity, i.e. a spin state >1, in particular from anexcited triplet state. In the sense of this application, all luminescentcomplexes containing transition metals or lanthanides, in particular alliridium, platinum and copper complexes, are to be regarded asphosphorescent compounds.

The mixture of the compound according to the invention and the emittingcompound comprises between 99 and 1% by vol., preferably between 98 and10% by vol., particularly preferably between 97 and 60% by vol., inparticular between 95 and 80% by vol., of the compound according to theinvention, based on the entire mixture comprising emitter and matrixmaterial. Correspondingly, the mixture comprises between 1 and 99% byvol., preferably between 2 and 90% by vol., particularly preferablybetween 3 and 40% by vol., in particular between 5 and 20% by vol., ofthe emitter, based on the entire mixture comprising emitter and matrixmaterial.

A further preferred embodiment of the present invention is the use ofthe compound according to the invention as matrix material for aphosphorescent emitter in combination with a further matrix material.Particularly suitable matrix materials which can be employed incombination with the compounds according to the invention are aromaticketones, aromatic phosphine oxides or aromatic sulfoxides or sulfones,for example in accordance with WO 2004/013080, WO 2004/093207, WO2006/005627 or WO 2010/006680, triarylamines, carbazole derivatives, forexample CBP (N,N-bis-carbazolylbiphenyl) or the carbazole derivativesdisclosed in WO 2005/039246, US 2005/0069729, JP 2004/288381, EP1205527, WO 2008/086851 or the unpublished application EP 11007693.2,indolocarbazole derivatives, for example in accordance with WO2007/063754 or WO 2008/056746, indenocarbazole derivatives, for examplein accordance with WO 2010/136109 or WO 2011/000455, azacarbazolederivatives, for example in accordance with EP 1617710, EP 1617711, EP1731584, JP 2005/347160, bipolar matrix materials, for example inaccordance with WO 2007/137725, silanes, for example in accordance withWO 2005/111172, azaboroles or boronic esters, for example in accordancewith WO 2006/117052, triazine derivatives, for example in accordancewith WO 2007/063754, WO 2008/056746, WO 2010/015306, WO 2011/057706, WO2011/060859 or WO 2011/060877, zinc complexes, for example in accordancewith EP 652273 or WO 2009/062578, diazasilole or tetraazasilolederivatives, for example in accordance with WO 2010/054729,diaza-phosphole derivatives, for example in accordance with WO2010/054730, bridged carbazole derivatives, for example in accordancewith WO 2011/042107, WO 2011/060867, WO 2011/088877 and the unpublishedapplication EP 11003232.3, or triphenylene derivatives, for example inaccordance with the unpublished application DE 102010048608.6. A furtherphosphorescent emitter which emits at shorter wavelength than the actualemitter may likewise be present in the mixture as co-host.

Suitable phosphorescent compounds (=triplet emitters) are, inparticular, compounds which emit light, preferably in the visibleregion, on suitable excitation and in addition contain at least one atomhaving an atomic number greater than 20, preferably greater than 38 andless than 84, particularly preferably greater than 56 and less than 80,in particular a metal having this atomic number. The phosphorescenceemitters used are preferably compounds which contain copper, molybdenum,tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium,platinum, silver, gold or europium, in particular compounds whichcontain iridium or platinum.

Examples of the emitters described above are revealed by theapplications WO 00/70655, WO 2001/41512, WO 2002/02714, WO 2002/15645,EP 1191613, EP 1191612, EP 1191614, WO 2005/033244, WO 2005/019373, US2005/0258742, WO 2010/086089, WO 2011/157339 and WO 2012/007086. Alsosuitable are, for example, the metal complexes disclosed in theunpublished applications EP 11004545.7, EP 11005252.9 and EP 11006562.0.In general, all phosphorescent complexes as are used in accordance withthe prior art for phosphorescent OLEDs and as are known to the personskilled in the art in the area of organic electroluminescence aresuitable, and the person skilled in the art will be able to use furtherphosphorescent complexes without inventive step.

In a further embodiment of the invention, the organic electroluminescentdevice according to the invention does not comprise a separatehole-injection layer and/or hole-transport layer and/or hole-blockinglayer and/or electron-transport layer, i.e. the emitting layer isdirectly adjacent to the hole-injection layer or the anode, and/or theemitting layer is directly adjacent to the electron-transport layer orthe electron-injection layer or the cathode, as described, for example,in WO 2005/053051. It is furthermore possible to use a metal complexwhich is the same as or similar to the metal complex in the emittinglayer as hole-transport or hole-injection material directly adjacent tothe emitting layer, as described, for example, in WO 2009/030981.

In a further embodiment of the invention, the compound according to theinvention is employed in a hole-transport layer or in anelectron-blocking layer or exciton-blocking layer.

In still a further preferred embodiment of the invention, the compoundaccording to the invention is employed as electron-transport material inan electron-transport or electron-injection layer. The emitting layerhere may be fluorescent or phosphorescent. If the compound is employedas electron-transport material, it may be preferred for it to be doped,for example with alkali-metal complexes, such as, for example, LiQ(lithium hydroxy-quinolinate).

In still a further preferred embodiment of the invention, the compoundaccording to the invention is employed in a hole-blocking layer. Ahole-blocking layer is taken to mean a layer which is directly adjacentto an emitting layer on the cathode side.

In the further layers of the organic electroluminescent device accordingto the invention, all materials can be used as are usually employed inaccordance with the prior art. The person skilled in the art willtherefore be able to employ all materials which are known for organicelectroluminescent devices in combination with the compounds of theformula (1) according to the invention or the preferred embodimentsindicated above without inventive step.

Preference is furthermore given to an organic electroluminescent device,characterised in that one or more layers are coated by means of asublimation process, in which the materials are applied by vapourdeposition in vacuum sublimation units at an initial pressure of lessthan 10⁻⁵ mbar, preferably less than 10⁻⁶ mbar. However, it is alsopossible for the initial pressure to be even lower, for example lessthan 10⁻⁷ mbar.

Preference is likewise given to an organic electroluminescent device,characterised in that one or more layers are coated by means of the OVPD(organic vapour phase deposition) process or with the aid of carrier-gassublimation, in which the materials are applied at a pressure between10⁻⁵ mbar and 1 bar. A special case of this process is the OVJP (organicvapour jet printing) process, in which the materials are applieddirectly through a nozzle and are thus structured (for example M. S.Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).

Preference is furthermore given to an organic electroluminescent device,characterised in that one or more layers are produced from solution,such as, for example, by spin coating, or by means of any desiredprinting process, such as, for example, screen printing, flexographicprinting, offset printing, LITI (light induced thermal imaging, thermaltransfer printing), ink-jet printing or nozzle printing. Solublecompounds, which are obtained, for example, by suitable substitution,are necessary for this purpose.

Also possible are hybrid processes, in which, for example, one or morelayers are applied from solution and one or more further layers areapplied by vapour deposition.

These processes are generally known to the person skilled in the art andcan be applied by him without inventive step to organicelectroluminescent devices comprising the compounds according to theinvention.

The compounds according to the invention and the organicelectroluminescent devices according to the invention are distinguishedby one or more of the following surprising advantages over the priorart:

-   1. The compounds according to the invention or compounds of the    formula (1) or the preferred embodiments indicated above, employed    as matrix material for fluorescent or phosphorescent emitters,    result in high efficiencies and in long lifetimes. This applies, in    particular, if the compounds are employed as matrix material for a    phosphorescent emitter.-   2. The compounds according to the invention or compounds of the    formula (1) or the preferred embodiments indicated above are    suitable not only as matrix for red-phosphorescent compounds, but    also for green- and possibly also for blue-phosphorescent compounds.-   3. The compounds according to the invention can be prepared in very    high yield and very high purity, which means that complex    purification, which is always also associated with losses of    material, can be omitted or at least is only necessary to a    considerably reduced extent.-   4. The compounds according to the invention have high thermal    stability, which offers advantages not only in the production of the    OLEDs by vacuum evaporation, but also in the purification by    sublimation methods.

These above-mentioned advantages are not accompanied by an impairment inthe other electronic properties.

The invention is explained in greater detail by the following exampleswithout wishing to restrict it thereby. The person skilled in the artwill be able to use the descriptions to carry out the inventionthroughout the range disclosed and prepare further compounds accordingto the invention without inventive step and use them in electronicdevices or apply the process according to the invention.

EXAMPLES

The following syntheses are carried out, unless indicated otherwise,under a protective-gas atmosphere in dried solvents. The solvents andreagents can be purchased from ALDRICH or ABCR. The numbers indicated inthe case of the starting materials which are not commercially availableare the corresponding CAS numbers.

Example 1 2,7-Dibromosipro-9,9′-bixanthene, synthone S1

The corresponding Grignard reagent is prepared from 95.6 g (380 mmol) of2-bromophenyl phenyl ether [7025-06-1] in a mixture of 2.6 ml (34 mmol)of 1,2-dichloroethane and 1000 ml of THF with 10.8 g (410 mmol) ofiodine-activated magnesium turnings. When all the magnesium has reacted,112.0 g (316 mmol) of 2,7-dibromoxanthone[40102-85-0] in solid form areintroduced into the solution in portions, and the reaction mixture isstirred under reflux for a further 6 h. 500 ml of THF are distilled off,the suspension is allowed to cool to 30° C. with stirring, 900 ml ofglacial acetic acid are rapidly added dropwise (NOTE: exothermic!), amixture of 100 ml of glacial acetic acid and 30 ml of conc. sulfuricacid is added dropwise to the red solution, the mixture is stirred at60° C. for a further 6 h, allowed to cool to 30° C., 600 ml of ethanoland then 400 ml of a mixture of ethanol:water (1:1 v:v) are addeddropwise, the mixture is stirred for a further 1 h, the colourless solidis filtered off with suction, washed twice with 150 ml of glacial aceticacid each time, twice with 200 ml of a mixture of ethanol:water (1:1v:v) each time and dried in vacuo. The solid is taken up in 2000 ml ofdichloromethane, insoluble components are filtered off with suction viaa short Celite bed, the dichloromethane is removed in vacuo, and theproduct is then recrystallised once from DMF. Yield: 121.6 g (240 mmol),76%; purity: about 99.5% according to ¹H-NMR.

The following compounds are obtained analogously:

Bromo- Ex. diaryl ether Xanthone Product Yield 2

  861548-92-7

  S2 73% 3

  500286-36-2

  S3 78% 4

  56341-31-2

  S4 77% 5

  1246661-43-7

  S5 68% 6

  27044-93-5

  S6 70% 7

  556113-49-6

  S7 66%

Example 8 2,7-Bis(diphenylamino)sipro-9,9′-spirobixanthene

A mixture of 50.6 g (100 mmol) of 2,7-dibromospiro-9,9′-spirobixantheneS1, 37.2 g (220 mmol) of diphenylamine, 25.0 g (260 mmol) of sodiumtert-butoxide, 809 mg (4 mmol) of tri-tert-butylphosphine, 449 mg (2mmol) of palladium(II) acetate and 1000 ml of toluene is heated underreflux for 16 h. The reaction mixture is allowed to cool to 50° C., 500ml of water are added, the organic phase is separated off, washed twicewith 500 ml of water, dried over magnesium sulfate, filtered through aCelite bed (5 cm) and then evaporated to dryness in vacuo. The crudeproduct is recrystallised twice from DMF and three times from dioxaneand finally subjected to fractional sublimation twice (p about 10⁻⁵mbar, T=330° C.). Yield: 32.9 g (48 mmol) 48%, purity: 99.9% accordingto HPLC.

The following compounds are obtained analogously, using 200 mmol in thecase of monobromides:

Ex. Amine Bromide Product Yield  9

  102113-98-4

  S1

45% 10

  897671-69-1

  S1

51% 11

  1198395-24-2

  S1

44% 12

  102113-98-4

  S2

50% 13

  169224-65-1

  S2

46% 14

  S3

45% 15

  S3

46% 16

  1198395-24-2

  S4

41% 17

  5369-25-5

  S4

49% 18

  1198395-24-2

  S5

42% 19

  1198395-24-2

  S6

46% 20

  86-74-8

  S2

  Potassium carbonate is used instead of sodium tert- butoxide, o-xyleneis used instead of toluene. 50% 21

  1257220-47-5

  S3

  Potassium carbonate is used instead of sodium tert- butoxide, o-xyleneis used instead of toluene. 38%

Example 22 2,7-Dibromosipro-9,9′-spirobixanthene

40 ml (100 mmol) of n-butyllithium (2.5M in n-hexane) are added dropwiseto a solution, cooled to −78° C., of 42.7 g (100 mmol) of2-bromospiro-9,9′-spirobixanthene S4 in 1500 ml of THF, and the mixtureis stirred for a further 30 min. 4.6 ml (50 mmol) ofN,N-dimethylcarbamoyl chloride [79-44-7], diluted with 10 ml of THF, arethen added in one portion, the reaction mixture is stirred for a further30 min., allowed to warm to 0° C., 50 ml of conc. hydrochloric acid areadded, and the reaction mixture is heated under reflux for 5 h. Aftercooling, the THF is removed in vacuo, the residue is taken up in 200 mlof ethanol, rendered weakly alkaline using 10% ammonia solution, thesolid which has precipitated out is filtered off with suction, washedthree times with 100 ml of an ethanol/water mixture (1:1 vv) each timeand finally washed once with 50 ml of ethanol. The crude product isrecrystallised five times from DMF and finally subjected to fractionalsublimation twice (p about 10⁻⁵ mbar, T=340° C.). Yield: 19.5 g (27mmol) 54%, purity: 999% according to HPLC.

The following compounds are obtained analogously:

Ex. Electrophile Bromide Product Yield 23

  S3

57% 24

  1351669-38-9 100 mmol of electrophile

  S2

  The hydrolysis step with conc. HCl is omitted. 42% 25

  1499-21-4

  S3

  The hydrolysis step with conc. HCl is omitted. 58% 26

  1205748-61-3 100 mmol of electrophile

  S3

  The hydrolysis step with conc. HCl is omitted. 53%Production of the OLEDs

OLEDs according to the invention and OLEDs in accordance with the priorart are produced by a general process in accordance with WO 2004/058911,which is adapted to the circumstances described here (layer-thicknessvariation, materials).

The structure and data of various OLEDs are presented in the followingExamples O1 to O22 (see Tables 1 to 5). Glass plates coated withstructured ITO (indium tin oxide) in a thickness of 150 nm are coatedwith 20 nm of PEDOT (poly(3,4-ethylenedioxy-2,5-thiophene), applied byspin coating from water; purchased from H. C. Starck, Goslar, Germany)for improved processing. These coated glass plates form the substratesto which the OLEDs are applied. The OLEDs have in principle thefollowing layer structure: substrate/optional hole-injection layer(HIL)/hole-transport layers (HTL)/interlayer (IL)/electron-blockinglayer (EBL)/emission layer (EML)/electron-transport layer (ETL)/optionalelectron-injection layer (EIL) and finally a cathode. The cathode isformed by an aluminium layer with a thickness of 100 nm. The precisestructure of the OLEDs is shown in Tables 1 and 3. The materialsrequired for the production of the OLEDs are shown in Table 5.

All materials are applied by thermal vapour deposition in a vacuumchamber. The emission layer here always consists of at least one matrixmaterial (host material) and an emitting dopant (emitter), which isadmixed with the matrix material or matrix materials in a certainproportion by volume by co-evaporation. An expression such as H1:SEB1(95%:5%) here means that material H1 is present in the layer in aproportion by volume of 95% and SEB1 is present in the layer in aproportion of 5%. Analogously, the electron-transport layer may alsoconsist of a mixture of two materials.

The OLEDs are characterised by standard methods. For this purpose, theelectroluminescence spectra, the current efficiency (measured in cd/A),the power efficiency (measured in Im/W) and the external quantumefficiency (EQE, measured in percent) as a function of the luminousdensity, calculated from current/voltage/luminous density characteristiclines (IUL characteristic lines) assuming Lambert emissioncharacteristics, and the lifetime are determined. Theelectroluminescence spectra are determined at a luminous density of 1000cd/m², and the CIE 1931 x and y colour coordinates are calculatedtherefrom. The term U @ 1000 cd/m² in Table 2 and 4 denotes the voltagerequired for a luminous density of 1000 cd/m². Finally, EQE @ 1000 cd/m²denotes the external quantum efficiency at an operating luminous densityof 1000 cd/m². LT80 @ 6000 cd/m2 is the lifetime until the OLED at aluminosity of 6000 cd/m² has dropped to 80% of the initial intensity,i.e. to 4800 cd/m².

The data measured for the various OLEDs are summarised in Tables 2 and4.

Use of the Compounds According to the Invention in Fluorescent andPhosphorescent OLEDs

The compounds according to the invention are suitable, in particular, asHTM (hole-transport material) or EBM (electron-blocking material) inOLEDs. They are suitable for use in a single layer, but also ascomponent of a mixture as HTM, EBM or as constituent of the emittinglayer. Compared with comparative devices in accordance with the priorart (V1 and V2), all samples comprising the compounds according to theinvention exhibit higher efficiencies and/or improved lifetimes.Compared with reference material NPB, the compounds according to theinvention exhibit better efficiencies and better lifetimes.

TABLE 1 Structure of the OLEDs IL HTL IL HTL2 EBL EML ETL Ex.Thickness/nm Thickness/nm Thickness/nm Thickness/nm Thickness/nmThickness/nm Thickness/nm V1 HIL1 HIL2 HIL1 NPB NPB H1(95%):SEB1(5%)ETM1(50%):LiQ(50%) 5 nm 130 nm 5 nm 10 nm 20 nm 20 nm 30 nm O1 HIL1 HIL2HIL1 NPB Ex. 8 H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 130 nm 5 nm 10nm 20 nm 20 nm 30 nm O2 HIL1 HIL2 HIL1 — Ex. 9 H1(95%):SEB1(5%)ETM1(50%):LiQ(50%) 5 nm 130 nm 5 nm 30 nm 20 nm 30 nm O3 HIL1 HIL2 HIL1— Ex. 10 H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 130 nm 5 nm 20 nm 20nm 30 nm O4 HIL1 HIL2 HIL1 — Ex. 11 H1(95%):SEB1(5%) ETM1(50%):LiQ(50%)5 nm 130 nm 5 nm 30 nm 20 nm 30 nm O5 HIL1 HIL2 HIL1 — Ex. 12H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 130 nm 5 nm 30 nm 20 nm 30 nmO6 HIL1 HIL2 HIL1 — Ex. 13 H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 130nm 5 nm 30 nm 20 nm 30 nm O7 HIL1 HIL2 HIL1 — Ex. 14 H1(95%):SEB1(5%)ETM1(50%):LiQ(50%) 5 nm 130 nm 5 nm 30 nm 20 nm 30 nm O8 HIL1 HIL2 HIL1— Ex. 15 H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 130 nm 5 nm 30 nm 20nm 30 nm O9 HIL1 HIL2 HIL1 — Ex. 16 H1(95%):SEB1(5%) ETM1(50%):LiQ(50%)5 nm 130 nm 5 nm 30 nm 20 nm 30 nm O10 HIL1 HIL2 HIL1 — Ex. 17H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 130 nm 5 nm 30 nm 20 nm 30 nmO11 HIL1 HIL2 HIL1 — Ex. 18 H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 130nm 5 nm 30 nm 20 nm 30 nm O12 HIL1 HIL2 HIL1 — Ex. 19 H1(95%):SEB1(5%)ETM1(50%):LiQ(50%) 5 nm 130 nm 5 nm 30 nm 20 nm 30 nm

TABLE 2 Data of the OLEDs U EQE LT80 @ 1000 @ 1000 @ 6000 cd/m2 cd/m2cd/m² CIE Ex. V % [h] x y V1 4.7 4.8 70 0.14 0.17 O1 4.3 6.7 80 0.140.16 O2 4.3 6.6 100 0.14 0.16 O3 4.4 6.4 95 0.14 0.16 O4 4.4 7.2 1050.14 0.16 O5 4.4 6.9 120 0.14 0.16 O6 4.4 7.0 110 0.14 0.16 O7 4.5 7.0120 0.14 0.16 O8 4.4 7.1 125 0.14 0.16 O9 4.6 7.3 130 0.14 0.16 O10 4.66.7 85 0.14 0.16 O11 4.3 7.1 115 0.14 0.16 O12 4.5 7.0 120 0.14 0.16

TABLE 3 Structure of the OLEDs HTL IL HTL2 EBL EML ETL Ex. Thickness/nmThickness/nm Thickness/nm Thickness/nm Thickness/nm Thickness/nm V2 HIL2HIL1 — NPB H2(88%):Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 90 nm 30 nm40 nm O13 HIL2 HIL1 — Ex. 14 H2(88%):Irpy(12%) ETM1(50%):LiQ(50%) 70 nm5 nm 80 nm 30 nm 40 nm O14 HIL2 HIL1 — Ex. 15 H2(88%):Irpy(12%)ETM1(50%):LiQ(50%) 70 nm 5 nm 80 nm 30 nm 40 nm O15 HIL2 HIL1 — Ex. 15H3(30%):Ex. ETM1(50%):LiQ(50%) 70 nm 5 nm 90 nm 22(65%):Irpy(5%) 40 nm30 nm O16 HIL2 HIL1 — Ex. 15 H3(20%):Ex. ETM1(50%):LiQ(50%) 70 nm 5 nm90 nm 23(75%):Irpy(5%) 40 nm 30 nm O17 HIL2 HIL1 — Ex. 15 H3(30%):Ex.ETM1(50%):LiQ(50%) 70 nm 5 nm 90 nm 24(65%):Irpy(5%) 40 nm 30 nm O18HIL2 HIL1 — Ex. 15 H3(30%):Ex. ETM1(50%):LiQ(50%) 70 nm 5 nm 90 nm25(65%):Irpy(5%) 40 nm 30 nm O19 HIL2 HIL1 — Ex. 15 H3(25%):Ex.ETM1(50%):LiQ(50%) 70 nm 5 nm 90 nm 26(70%):Irpy(5%) 40 nm 30 nm O20HIL2 HIL1 — Ex. 15 Ex. 15(30%):Ex. ETM1(50%):LiQ(50%) 70 nm 5 nm 90 nm26(65%):Irpy(5%) 40 nm 30 nm O21 HIL2 HIL1 — Ex. 14 Ex.20(88%):Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 80 nm 30 nm 40 nm O22HIL2 HIL1 — Ex. 14 Ex. 21(88%):Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm80 nm 30 nm 40 nm

TABLE 4 Data of the OLEDs U EQE LT80 @ 1000 @ 1000 @ 8000 cd/m2 cd/m2cd/m² CIE Ex. V % [h] x y V2 3.5 14.4 90 0.32 0.63 O13 3.3 18.5 120 0.330.63 O14 3.3 18.7 130 0.33 0.63 O15 3.2 18.9 140 0.33 0.64 O16 3.3 19.0150 0.33 0.63 O17 3.3 18.4 110 0.33 0.64 O18 3.6 18.7 105 0.33 0.63 O193.4 18.7 140 0.33 0.63 O20 3.2 18.8 135 0.33 0.64 O21 3.4 18.0 90 0.330.64 O22 3.4 18.3 125 0.33 0.64

TABLE 5

  HIL1

  HIL2

  NPB

  ETM1

  Alq3

  H1

  SEB1

  LiQ

  H2

  H3

  Irpy

The invention claimed is:
 1. A compound of the formula (1),

where the following applies to the symbols and indices used: X is oneach occurrence, identically or differently, CR¹ or N; where a maximumof one group X per ring stands for N; or two adjacent X stand for agroup of the following formula (3),

where ^ indicates the corresponding adjacent groups X in the formula(1); X here stands for C if a group Ar or L is bonded to this group X; Vis on each occurrence, identically or differently, C(R¹)₂, or NR¹; Z ison each occurrence, identically or differently, CR¹; Ar is on eachoccurrence, identically or differently, an aromatic or heteroaromaticring system having 5 to 40 aromatic ring atoms, which can be substitutedby one or more radicals R²; the group Ar and the adjacent group X, whichin this case stands for C, can also be bridged to one another here by asingle bond or a divalent group selected from C(R²)₂, NR², O or S; L ison each occurrence, identically or differently, a single bond or adivalent group; R¹ and R² is selected on each occurrence, identically ordifferently, from the group consisting of H, D, F, Cl, Br, I, CN, NO₂,N(Ar¹)₂, N(R³)₂, C(═O)Ar¹, C(═O)R³, P(═O)(Ar¹)₂, B(Ar¹)₂, Si(Ar¹)₃,Si(R³)₃, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl grouphaving 3 to 40 C atoms or an alkenyl or alkynyl group having 2 to 40 Catoms, each of which can be substituted by one or more radicals R³,where one or more non-adjacent CH₂ groups can be replaced by R³C═CR³,C≡C, Si(R³)₂, C═O, C═S, C═NR³, P(═O)(R³), SO, SO₂, NR³, O, S or CONR³and where one or more H atoms can be replaced by D, F, Cl, Br, I, CN orNO₂, an aromatic or heteroaromatic ring system having 5 to 60 aromaticring atoms, which can in each case be substituted by one or moreradicals R³, an aryloxy or heteroaryloxy group having 5 to 60 aromaticring atoms, which can be substituted by one or more radicals R³, wheretwo or more adjacent substituents R¹ or R² can optionally form amonocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ringsystem, which can be substituted by one or more radicals R³; wherein ifR¹ or R² stand for an aromatic or heteroaromatic ring system, this isselected, identically or differently on each occurrence, from benzene,ortho-, meta- or para-biphenyl, ortho-, meta-, para- or branchedterphenyl, ortho-, meta- para- or branched quaterphenyl, 1 or2-naphthyl, pyrrole, furan, thiophene, indole, benzofuran,benzothiophene, carbazole, dibenzofuran, dibenzothiophene, pyridine,pyrimidine, pyrazine, pyridazine, triazine, anthracene, phenanthrene,pyrene, benzanthracene or combinations of two or three of these groups,each of which can be substituted by one or more radicals R³, Ar¹ is oneach occurrence, identically or differently, an aromatic orheteroaromatic ring system having 5-30 aromatic ring atoms, which can besubstituted by one or more non-aromatic radicals R³; two radicals Ar¹here which are bonded to the same N atom or P atom can also be bridgedto one another by a single bond or a bridge selected from N(R³), C(R³)₂,O or S; R³ is selected on each occurrence, identically or differently,from the group consisting of H, D, F, Cl, Br, I, CN, NO₂, N(R⁴)₂,C(═O)R⁴, P(═O)(R⁴)₂, a straight-chain alkyl, alkoxy or thioalkyl grouphaving 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy orthioalkyl group having 3 to 40 C atoms or an alkenyl or alkynyl grouphaving 2 to 40 C atoms, each of which can be substituted by one or moreradicals R⁴, where one or more non-adjacent CH₂ groups can be replacedby R⁴C═CR⁴, C≡C, Si(R⁴)₂, C═O, C═S, C═NR⁴, P(═O)(R⁴), SO, SO₂, NR⁴, O, Sor CONR⁴ and where one or more H atoms can be replaced by D, F, Cl, Br,I, CN or NO₂, an aromatic or heteroaromatic ring system having 5 to 60aromatic ring atoms, which can in each case be substituted by one ormore radicals R⁴, an aryloxy or heteroaryloxy group having 5 to 60aromatic ring atoms, which can be substituted by one or more radicalsR⁴, or a combination of these systems, where two or more adjacentsubstituents R³ can optionally form a monocyclic or polycyclic,aliphatic ring system, which can be substituted by one or more radicalsR⁴; R⁴ is selected on each occurrence, identically or differently, fromthe group consisting of H, D, F, CN, an aliphatic hydrocarbon radicalhaving 1 to 20 C atoms, an aromatic or heteroaromatic ring system having5 to 30 aromatic ring atoms, in which one or more H atoms can bereplaced by D, F, Cl, Br, I or CN, where two or more adjacentsubstituents R⁴ can form a mono- or polycyclic, aliphatic ring systemwith one another; m is on each occurrence, identically or differently, 0or 1; n is 0, 1, 2, 3, 4 or 5; with the proviso that for n=0, at leastone substituent R¹ is present which is selected from the groupconsisting of CN, N(Ar¹)₂, C(═O)Ar¹, P(═O)(Ar¹)₂, B(Ar¹)₂, Si(Ar¹)₃,Si(R³)₃ or an aromatic or heteroaromatic ring system having 5 to 60aromatic ring atoms, which can in each case be substituted by one ormore radicals R³; compounds of the formula (1) in which n=0 and foursubstituents R¹ stand, identically or differently, for an optionallysubstituted carbazole or diphenylamine, which is in each case bonded tothe skeleton via the nitrogen atom, are excluded.
 2. The compoundaccording to claim 1, wherein the compound is selected from thecompounds of the formula (1a), (1b), (1c) or (1d),


3. The compound according to claim 1, wherein the compound is of one ofthe formulae (5) to (8),


4. A compound selected from the compounds of the formulae (5a) to (5u),

R¹ is selected on each occurrence, identically or differently, from thegroup consisting of H, D, F, Cl, Br, I, CN, NO₂, N(Ar¹)₂, N(R³)₂,C(═O)Ar¹, C(═O)R³, P(═O)(Ar¹)₂, B(Ar¹)₂, Si(Ar¹)₃, Si(R³)₃, astraight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atomsor a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms, each ofwhich can be substituted by one or more radicals R³, where one or morenon-adjacent CH₂ groups can be replaced by R³C═CR³, C≡C, Si(R³)₂, C═O,C═S, C═NR³, P(═O)(R³), SO, SO₂, NR³, O, S or CONR³ and where one or moreH atoms can be replaced by D, F, Cl, Br, I, CN or NO₂, an aromatic orheteroaromatic ring system having 5 to 60 aromatic ring atoms, which canin each case be substituted by one or more radicals R³, an aryloxy orheteroaryloxy group having 5 to 60 aromatic ring atoms, which can besubstituted by one or more radicals R³, where two or more adjacentsubstituents R¹ or R² can optionally form a monocyclic or polycyclic,aliphatic, aromatic or heteroaromatic ring system, which can besubstituted by one or more radicals R³; Ar¹ is on each occurrence,identically or differently, an aromatic or heteroaromatic ring systemhaving 5-30 aromatic ring atoms, which can be substituted by one or morenon-aromatic radicals R³; two radicals Ar¹ here which are bonded to thesame N atom or P atom can also be bridged to one another by a singlebond or a bridge selected from N(R³), C(R³)₂, O or S; R³ is selected oneach occurrence, identically or differently, from the group consistingof H, D, F, Cl, Br, I, CN, NO₂, N(R⁴)₂, C(═O)R⁴, P(═O)(R⁴)₂, astraight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atomsor a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms, each ofwhich can be substituted by one or more radicals R⁴, where one or morenon-adjacent CH₂ groups can be replaced by R⁴C═CR⁴, C≡C, Si(R⁴)₂, C═O,C═S, C═NR⁴, P(═O)(R⁴), SO, SO₂, NR⁴, O, S or CONR⁴ and where one or moreH atoms can be replaced by D, F, Cl, Br, I, CN or NO₂, an aromatic orheteroaromatic ring system having 5 to 60 aromatic ring atoms, which canin each case be substituted by one or more radicals R⁴, an aryloxy orheteroaryloxy group having 5 to 60 aromatic ring atoms, which ma besubstituted by one or more radicals R⁴, or a combination of thesesystems, where two or more adjacent substituents R³ can optionally forma monocyclic or polycyclic, aliphatic ring system, which can besubstituted by one or more radicals R⁴; R⁴ is selected on eachoccurrence, identically or differently, from the group consisting of H,D, F, CN, an aliphatic hydrocarbon radical having 1 to 20 C atoms, anaromatic or heteroaromatic ring system having 5 to 30 aromatic ringatoms, in which one or more H atoms can be replaced by D, F, Cl, Br, Ior CN, where two or more adjacent substituents R⁴ can form a mono- orpolycyclic, aliphatic ring system with one another, with the provisothat for n=0, at least one substituent R¹ is present which is selectedfrom the group consisting of CN, N(Ar¹)₂, C(═O)Ar¹, P(═O)(Ar¹)₂,B(Ar¹)₃, Si(Ar¹)₃, Si(R³)₃ or an aromatic or heteroaromatic ring systemhaving 5 to 60 aromatic ring atoms, which can in each case besubstituted by one or more radicals R³.
 5. The compound according toclaim 1, wherein the compound is substituted by at least one group—C(═O)Ar¹ or —P(═O)(Ar¹)₂ or an electron-deficient heteroaromatic ringsystem, where at least one substituent R¹ and/or R² or a monovalentgroup Ar is selected from structures of the formula (13) to (16) for R¹or R² or the formulae (17), (18) or (19) for Ar,

and/or at least one divalent or trivalent group Ar stands for a group ofthe formulae (17) to (19),

where R⁴ and m have the meaning given in claim 1, * indicates theposition of the bonding of the group of the formula (13) to (19) andfurthermore: A is on each occurrence, identically or differently, CR⁴ orN, with the proviso that one, two or three groups A stand for N; Ar² is,identically or differently on each occurrence, a divalent aromatic orheteroaromatic ring system having 5 to 16 C atoms, which can besubstituted by one or more radicals R⁴.
 6. The compound of claim 1,wherein the compound is substituted by at least one group which can besubstituted by R³, or at least one substituent R¹ or R² stands forN(Ar¹)₂, where these groups are selected from group of the followingformulae (35)-(49):

E is selected from the group consisting of C(R³)₂, NR³, O or S; and G isselected from the group consisting of NR³, O or S; * indicates theposition of the bonding of the group of the formulae (35) to (49), Ar²is, identically or differently on each occurrence, a divalent aromaticor heteroaromatic ring system having 5 to 16 C atoms, which can besubstituted by one or more radicals R⁴.
 7. A process for the preparationof the compound according to claim 1, comprising the reaction steps of:a) synthesising a halogen-substituted spiro-9,9-bixanthene; and b)reacting the halogen-substituted spiro-9,9-bixanthene in a C—C coupling,C—N coupling, sililyation, phosphanylation, boranylation orpolycondensation.
 8. An oligomer, polymer or dendrimer containing one ormore compounds according to claim 1, where one or more bonds from thecompound to the polymer, oligomer or dendrimer are present instead ofsubstituents at one or more positions.
 9. An electronic device whichcomprises the compound according to claim
 1. 10. The electronic deviceas claimed in claim 9, wherein the electronic device is selected fromthe group consisting of organic electroluminescent device, organicintegrated circuit, organic field-effect transistor, organic thin-filmtransistor, organic light-emitting transistor, organic solar cell,dye-sensitised organic solar cell, organic optical detector, organicphotoreceptor, organic field-quench device, light-emittingelectrochemical cell, organic laser diode and organic plasmon emittingdevice.
 11. An organic electroluminescent device which comprises thecompound according to claim 1 as matrix material for fluorescent orphosphorescent emitters and/or as fluorescent emitter and/or in anelectron-blocking or exciton-blocking layer and/or in a hole-transportlayer and/or in a hole-injection layer and/or in a hole-blocking layerand/or in an electron-transport layer, depending on the precisesubstitution.